The convergent biomimetic gram-scale synthesis of disesquiterpenoid ester rumphellolide J is described. 4β,8β-Epoxycaryophyllan-5-ol was prepared in 67% yield (1.4 g) from naturally ambudant (–)-β-caryophyllene. (+)-Rumphellaoic acid A was obtained in...
The first semisynthetic route toward
rumphellaones B (2) and C (3) and their
C-8 epimers as well as the shortest
synthesis of rumphellaone A (1) and its C-8 epimer from
the most accessible sesquiterpene, β-caryophyllene (4), is presented. Synthetic routes involved caryophyllonic acid as
a key intermediate, which was converted to rumphellaone A (and epimer)
via acid-catalyzed lactonization and rumphellaone C (and epimer) using
one-pot epoxidation–lactonization. Rumphellaone B (2) and its epimer were obtained from rumphellaone A (1) and its epimer, respectively, using Saegusa–Ito oxidation.
The absolute configuration at C-8 was confirmed by single-crystal
X-ray analysis of rumphellaone B (2) and an acylated
derivative of rumphellaone C.
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